JPS58149969A - Energetic ray curing printing ink composition - Google Patents

Abstract

PURPOSE:To provide the titled printing ink compsn. which consists of a specified reaction product, a (meth) acrylic ester monomer and a radical polymerization initiator, is excellent in adhesion to substrate and workability and is suitable for offset printing. CONSTITUTION:The printing ink compsn. is prepared by blending (A) 10-80wt% reaction product obtained by interaction of (a) epoxy compd. containing at least one epoxy group in one molecule and having a molecular weight of 200-4,000 (e.g. glycidyl ether type epoxy resin) and (b) 90-20wt% non-radical-polymerizing monocarboxylic acid (e.g. acetic acid) at 70-300 deg.C, (B) 90-20wt% (meth) acrylic ester monomer of the formula where R1 is H, methyl, propyl or butyl; R2 is H or methyl; X is (alkyl)benzene ring or bisphenol residue; n is 1-10 and (C) 0-30wt% radical-polymerization initiator (e.g. benzoin).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an active energy ray-curable printing ink composition. The present invention relates to a curable printing ink composition which has excellent adhesion to a substrate and excellent properties such as foldability, and is also suitable for offset printing when used in an offset ink.

In recent years, research on compositions curable by active energy rays has been actively conducted, and among these, practical application is progressing in fields such as printing inks. These are composed of prepolymers and monomers having radical polymerizability, and radical polymerization initiators as necessary.The prepolymers are alkyd acrylates, polyester acrylates, epoxy acrylates, urethane-modified quecrylates, etc., and the monomers are In this case, acrylates of aliphatic alcohols, acrylates of alkylene oxide adducts of phenolic hydroxyl groups, acrylates of glycidyl compounds, etc. were used.

Alkyd acrylates are plasticized by resin acids,
The cured film is softened and has poor solvent resistance.

Although epoxy acrylate has excellent curability, it has poor adhesive properties, and when used in offset printing inks, it has the disadvantage of poor offset printing suitability such as dot reproducibility. In addition, acrylate using a polyisocyanate medium of fatty acid-modified alkyd has poor workability because it becomes highly viscous due to the urethane bonds in the molecule. Addition 1: It has the disadvantage of deteriorating curability.

As described above, when these active energy ray-curable compositions are used as printing ink compositions, the adhesion may be insufficient depending on the target metal material and the type of various organic coating coated boards. In addition, there were problems with processing resistance such as bendability and punching properties, and furthermore, the suitability for offset printing was poor, so there were few products that could be used satisfactorily.

As a result of intensive research to improve these drawbacks, the present invention has invented an active energy beam-curable printing ink composition that has excellent curability and excellent processing resistance such as adhesion to substrates and bendability. I ended up doing it.

That is, the present invention is directed to (a) a reaction product of an epoxy compound having one or more epoxy groups per molecule and a monocarboxylic acid that does not have radical polymerizability; , In general formula (1), Rt is a hydrogen atom, methyl group, ethyl group, propyl group, < is a butyl group, R
2 is a hydrogen atom, < is a methyl group, X is a benzene ring,
Argylbenzene ring moL, <' represents a bisphenol residue, n represents an integer of 1 to 10, and y represents an integer of 1 to 4.

) In the present invention, the epoxy compound means one or more epoxy groups in one molecule, preferably 1.5 or more, and includes glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine. Type epoxy resin, linear aliphatic epoxide, alicyclic epoxy resin, etc. can be suitably used. Glycidyl ether type epoxy fats include bisphenol A diglycidyl ether, bisphenol A di-β methyl glycidyl ether, bisphenol F diglycidyl ether, water-added bisphenol A glycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, and novolak glycidyl. There are ethers, polyalkylene glycol diglycidyl ethers, epoxy urethane resins, etc. Glycidyl ester type epoxy resins include phthalic acid diglycidyl ester and dimer acid diglycidyl ester, etc. Glycidylamine type epoxy resins include triglycidyl isocyanurate etc. In addition, linear aliphatic epoxy resins include epoxidized polybutadiene and epoxidized soybean oil, and alicyclic epoxy resins include bis(3,4-epoxy-6-methylcyclohexylmethyl) acyl. -), 3.4-epoxy-
6-methylcyclohexylmethyl, 3,4-epoxy-
Examples include 6-methylcyclohexanecarboxylate.

Monocarboxylic acids that do not have radical polymerizability include aliphatic saturated basic acids such as formic acid, acetic acid, propionic acid, caproic acid, caprylic acid, lauric acid, and stearic acid, oleic acid, linoleic acid, lylunic acid, and eleostearin. Unsaturated basic acids such as acids, fatty acids such as dehydrated castor oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, tall oil fatty acids, castor oil fatty acids, rosin, rosin derivatives such as water-added rosin, benzoic acid,
Aromatic-basic acids such as t-butylbenzoic acid can be used.

The reaction between an epoxy compound and a monocarboxylic acid that does not have radical polymerizability can be carried out in the range of 70°C to 300°C under an inert gas flow, and 0.5 carboxyl groups per 1 equivalent of epoxy groups. It is preferable to react in an equivalent amount or more, and more preferably to also esterify the secondary OH group generated by the reaction of the epoxy group with the carboxyl group. When used in offset printing ink, a good catalyst is used. You can also do it. As a catalyst, an amine catalyst is used in the ring-opening reaction of epoxy groups20
It can be carried out at a high temperature of 0 to 300°C or 200°C using an acid catalyst.
You can also do it below. If necessary, a reaction solvent can be used to remove water produced by the reaction and to prevent the reaction from burning.

The compound represented by the general formula (1) is an acrylic acid or methacrylic acid ester monomer, which is obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a phenol such as phenol, alkylphenol, resorcinol, or bisphenol. It is a (meth)acrylic acid ester monomer obtained by esterifying.

In the present invention, when the active energy ray is ultraviolet rays, it is necessary to add a photosensitizer (radical polymerization initiator), such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-chloro Benzoin sensitizers such as benzoin and a-allylbenzoin; aryl ketone sensitizers such as benzophenone, P-methylpensophe/7, P-p clobenzophenone, methyl 0-benzoylbenzoate, and acetophenone; 4 .Dialkylaminoarylketone sensitizers such as 4'-bisdiethylaminobenzophenone, isoamyl P-dimethylaminobenzoate, and P-dimethylaminoacetophenone, and multicarbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products. These can be used alone or in appropriate combinations. These photosensitizers may be present in the composition in amounts ranging from 0 to 30
It can be used in a range of weight%, but preferably 0 to
A range of 15% by weight is desirable.

In the present invention, the blending ratio of (a) and (b) is not particularly limited, but is preferably ←) 10-80
(b) The blending ratio is 20 to 90% by weight.

If an epoxy compound (a) with a molecular weight lower than 200 is used, the viscosity of the resulting reaction product (a) will be low, so the amount of monomer (b) used will be reduced, and the strength of the cured film will be reduced. I get weak and angry. In addition, if a tube with a molecular weight exceeding 4000 is used, the viscosity of the reaction product obtained in (a) will increase, and therefore the amount of monomer (b) used will increase, resulting in an increase in crosslinking density and poor adhesiveness. Deterioration in workability is observed, which is not preferable.

The above-mentioned epoxy compounds can be used, but it is preferable to use bisphenol type epoxy compounds to particularly improve processability, and novolac type epoxy compounds are used when suitability for offset printing is important. is preferred. Therefore, the ratio of both can be changed depending on the quality required.

The softening point of the reaction product between the epoxy compound of component (a) and the monocarboxylic acid that does not have radical polymerizability is 120°C.
In the above case, a large amount of monomer (b) is used, and processability deteriorates. In addition, the reaction product of (a) is (
Gelation occurs in the diluted pheno with the monomer b), making it impossible to obtain the desired diluted pheno, which is a curable repeating composition.

In addition, in the present invention, Ti organic or inorganic pigments, extender pigments, plasticizers, 1 each of each [cypress fat, solvents, curing accelerators, antifoaming agents, surfactants, etc. are added. can do. In addition, other monomers and prepolymers may be used in combination without detracting from the effects of the present invention.

The present invention will be explained below using Example 9-1. All symbols in the example indicate the tf# part.

Production Example-1 470 parts of Epicor) 1001 (Bisphenol A type epoxy resin manufactured by Shell Chemical ■, Molecule 1i900), 530 parts of oleic acid, and 10 parts of xylene were charged into four Lof flasks equipped with a stirrer and a condenser directly connected to the separation tube, and N11
The reaction was carried out at 200 to 220° C. for 7 hours while blowing gas, and when the acid value reached 6.0, xylene was recovered to obtain resin (A).

The resin (A) was diluted with 50% diluted alcohol. (Hereafter, the resin viscosity will be measured and displayed using this method.) Production Example 2 Ebicor) 1004 (Shell Chemical T14g Bisphenol A41 Eve Epoxy Resin Molecule 1600) 450 parts, P-Z-% + 9-Pfk Benzoic Al-2, 5, 9 parts, xylene 10 parts 1 200 to 220 as in Production Example-1
The reaction was carried out at °C for 8 hours, and when the acid value reached 7.0, xylene was collected to obtain rosin (B). The viscosity of the resin (B) was Y. Further, the softening point was measured by a capillary method and was found to be 78°C.

Manufacture (7112 DEN431 (Dow Chemical ■ back novolac type eboxy stool fat, molecular weight 760) 183 parts, oleic acid 2
90 parts of benzoic acid, 230 parts of benzoic acid, 10 parts of xylene, and 0.7 parts of triethylenediamine were charged in the same manner as in Production Example 1.
The reaction was carried out at 170 to 190°C for 4 hours while blowing g gas into it, and when the acid value reached 4, the xylene gold was recovered and the resin (
c) was obtained. Resin (Cl was measured at viscosity E.

Production Example 4 210 parts of ADEKASIZER 〇-130F (Epoxidized soybean oil manufactured by Asahi Denka Co., Ltd., molecular weight 980), 440 parts of hydrogenated rosin, Kapro@! 50 g, 101 ut of xylene were prepared in the same manner as in Production Example 1, and reacted at 200 to 220°C for 7 hours.
When the acid value reaches 5.0, the xylene is collected and the tree Aft (
D) was obtained. The viscosity was measured at G.

Production Example 5 71.7 parts of Epikote 828 (bisphenol type epoxy resin manufactured by Shell Chemical, molecule T380), 28.3 parts of acrylic, 0.1 part of hydroquinone, 0.1 part of triethylenediamine were prepared using a reflux device and 4 stirrers. Pour into a flask, let it react at 90°C to 120°C for 15 to 20 hours while blowing air, bring the acid value to below 1, and pump it out.
Resin (made into a crane).

Production Example 6 20 parts of linseed oil fatty acid and 47 parts of trimethylolpropane were heated to an acid value of 5 at 240°C under a stream of N2 gas in a flask.
33 parts of phthalic anhydride was added and the reaction was carried out for 3 hours at the same temperature to obtain an alkyd with an excess of hydroxyl groups and an acid value of 5 and an OH value of 310. Next, 71.5 parts of this alkyd,
10 parts of cyclohexane, 28.5 parts of acrylic acid, 1.0 part of P-ensulfone, 0.0 parts of Hydro-IP/N.
One part was placed in a four-hole flask equipped with a reflux device, and reacted at 90 to 110° C. for 12 hours while blowing −+11 air. When the acid value reached 10, cyclohexane was removed at 110 to 120° C. for 2 hours. The obtained resin had an acid value of 8.2 and a viscosity of 20.
00 voids/25°C.

The compositions shown in Table 1 of Examples and Comparative Examples were applied to tin plates, TFS plates,
If an aluminum plate or a tin plate is coated with alkyd resin or vinyl resin, then acrylic resin paint is applied to each coated plate, printed with an RI tester at a coating weight of 3011F/100-, and then irradiated with a curtain beam type electron beam. Irradiate at 10 Mrad using a device to create a cured film,
Ta.

The results are shown in Table 2.

Samples 1, 3, 5, 7, 9, and 11 shown in Table 1 were printed on a tin plate coated with a vinyl primer using an R tester at a coating amount of 30 mgr/100 cdi, and immediately after that, a coating amount of 67 w/cm was applied. 2 with @ stable
It was placed on a 10a++ cutting conveyor under a kW high-pressure mercury lamp and dried by irradiation.

The results obtained are shown in Table 3.

Table 3 (Note) Continuous hardening: 9 IIK rubbed strongly with fingers, ζ Indicates the maximum speed at which no slipping can be achieved 〇 Samples obtained next - 1, 3, 5, 7, 9, 11 In order to examine the printability of the inks, each of these inks was used for offset printing on a Heidel KORI (Heidel KORI) monochrome printing machine.

At the same time, 10 grams of ink and 20 grams of tap water were forcibly emulsified using a homomixer at 3000 rpm, and excess water was removed.

The results of the amount of water and emulsification of the emulsified ink thus obtained deviate from Table 4.

[Note] Amount of water emulsification: 20-25 is optimal; if it is less than 2G, there will be too much water and it will be empty, and if it exceeds 25g, it will be emulsified on the machine and it will be empty.

Underwater: The numerical value is the amount of water added. For example, if the value is less than 18 and 18 to 26, smear V will come out and printing will not be possible, and if it exceeds 26, there will be excess water and poor transfer will occur.

Claims (1)

[Scope of Claims] 1 (a) An acrylic acid or methacrylic acid ester monomer represented by a reaction product of an epoxy compound having one or more epoxy groups per molecule and a monocarboxylic acid that does not have radical polymerizability. In the general formula (+), R1 is a hydrogen atom, a methyl group, or a propyl group, < is a butyl group, R2 is a hydrogen atom, < is a methyl group, and n is 1 to 10
, X represents a benzene ring, alkylbenzene 3 or a bisphenol residue, and y represents an integer of 1 to 4. ) Printing ink composition. 2. The active energy ray-curable printing composition according to claim 1, wherein the epoxy compound has a molecular weight of 200 to 4,000. 3. The active energy ray-curable printing ink composition according to claim 1 or 2, wherein the epoxy compound is at least one selected from bisphenol type epoxy compounds and novolac type epoxy compounds. 4. The active energy ray-curable printing ink composition according to any one of claims 1 to 3, wherein the reaction product of an epoxy compound and a monocarboxylic acid that does not have radical polymerizability has a softening point of 120°C or less. thing.